Anthraquevone triazine vat dyestuffs



United States Patent ANTHRAQUINONE TRIAZINE VAT DYESTUFFS Friedrich Ebel; Mannheim-Feudenheim; Walter Rupp,

Ludwigshafen (Rl1ine-0 ppau); and Walter Keller, Ludwigshafen (Rhiifi' Germany," assigr'iors to Badische Anilin 8a Soda-Fabrik Aktiengesellschai't, Ludwigshafen (Rhine), Germany No Drawingr Application May 27, 1954,

Serial No. 432,930

fiClaims. (Cl. 260-239) This invention relates to vat dyestuffs of the anthraquinone series, in particular to amide like compounds of 1 .4-diamino-2-acetylanthraguinone.

We have found that-valuable vat dyestuffs are obtained when 1 mol of a 2-phenyl-4.6 dichlor-1.3.5 triazine is condensed with 2 mols of l.4-diamino-2-acetylanthraquinone. Said triazines may contain in the phenyl nucleus one or two chlorine atoms or a methyl group of a methoxy group.

The reaction is preferably effected by heating the componentsin an inert solvent of high boilirigpoint until no more hydrogen halide escapes e. gi in nitrobenzene, dichlorbenzene or trichlorbenzene. The co-employment of an acid-binding. agent, such as potash; sodium acetate, sodium sulfi te or pyridine, is generallyspeaking unnecessary but their addition may be of advantage in some cases. The reaction temperature lies between 70"a'nd '250"C., generally between 120 and 210 C.

The relative proportions are chosen so that only the amino group on the 4-position of the 1.4-diamino-2-acetylanthraquinone reacts with the 2-phenyl-4.6-dichlor-l.3.5- triazine. This is the case when 1 mol of the 2-phenyl- 4.6-dichlor-1.3.5-triazine is heated with 2 mols of 1.4- diaminQ-Z-acetyIanthraquinone.

The dyestuffs obtained dye natural and regenerated cellulose, and also polyamide fibers from the vat. in uniform blue shades of high fastness properties.

The following examples will further-'illustfate this invention but the invention is not restricted tothese examples. The parts are'tby weight.

Example 1 A mixture of: 28 parts of. lz4i-diamino zraeetylanthraquinone and 600 parts of nitrobenzenetis heated to 100 C. and 11 partsof Z pIienyI 4IG dichlor-I.3f-triazine are then added.- The temperature of -tiiemixture is slowly raised to -170 6,. while stirring and -maintaihed fo'r-fZ hours; The reaction mixture is-- tlin allowed I: t cool, the separated dyestuliis l filtered ofi by suction; washed with methanol anddried at 80 There are obtained 29.6 parts of a blue microcrystalline powder which. dyes cotton"orregene'r'ated cellulose or olyamide fibers reddish blue shades from a black-red vat. The new dyestufl dissolves in concentrated sulfuric acid giving a greenbrown coloration.

Example 2 Into 600 parts of dry nitrobenzene, there are introduced 34 parts of 1.4-diamino-2-acetylanthraquinone and 15.6 parts of 2-(4'-chlorphenyl)-4.6-dichlor-1.3.5-triazine and the mixture is slowly heated to 170 C. while stirring. After stirring the mixture for further 2 hours at this temperature, it is allowed to cool. The separated dyestufi is filtered ofl' by suction, washed well with methanol and dried. There are obtained 36 parts of a blue microcrystalline powder, which dissolves in concentrated sulfuric acid giving a brown coloration and which dyes cotton, re-

Patented I FEB? 21 1956 generated cellulose, and polyamide fibers strong reddishblue shades from-a deep redwatf- Eafample 3 A mixt'ure of 28 parts of 1.4-diam'in0-2 -acetylanthraquinone, 12 parts of 2-(3-methylphenyl)-4.6-dichlor- 1.3.5 triaiine and 500" parts of nitrobenzene is slowly heated "to C. while stirring andthis temperature maintained "fol-2 hours. After cooling the separated dyestuflt' is filtered off by suction, washed well with methanol and 'dri'edi There are Obtainetl' ZG- parts ofa bln'e microcrysmlline =powder; which: dissolves in concentrated sulfuric-* acid giving. a greenish brown coloration and which dyes cotton,regenerated cellulose; oe 'polyaniide fibers blue shades from a nearly black vat.

If 12 parts of 2-(4-methylphenyl)-4.6-dichlor-1.3.5- triazine instead of the 3-isomer are employed there are obtained 28.5 parts of a blue vat dyestuff.

Example 4 A mixture of 28 parts of 1- .4-diamino-2-acetylanthraquinone, 12.8 parts of 2-(2f-methoxyphenyl)-4.6-dichlor- 1.3.5-triazine and 500 parts of nitrobenzene is slowly heated to 170 C. and this temperature is maintained for 2 hours. After cooling the separated dyestuif is filtered off by suction, washed with methanol and There are obtained 28 parts of ablue powder? which dissolves in concentrated sulfuric acid giving a greenish-brown coloration and which}; dyes cotton, iregenei ated cellulose or polyamide fibers blue shadesfrom a black-red vat.

Example 5 A mixture of 28 parts of l.4-diamino-2-acetylanthraquinone, 12.8 parts of 2-(3-methoxyphenyl)-4.6-dichlor- 1.3.5-triazine and 500 parts of nitrobenzene is slowly heated to 170 C. and this temperature is maintained for 2 hours. After cooling'irtheseparateddyestuffds filtered off by suction, washed with methanol and dried. There are obtained 28 parts of a blue powder which dissolves in concentrated sulfuric acid giving a greenish-brown coloration and which dyes cotton, regenerated cellulose or polyamide fibers blue shades from a black-red vat.

Example 6 A mixture of-28 parts of l.4-diamin6-2-acetylanthraquinone, 12.8 pafits -of--2-(4-methoxyphenyl)-4.6-dichlor- 1.3.5-triazine. and 500 parts ofnitrobenzene is slowly heated tor'l70" C1. and-t this temperature is maintained for 2 hours. After coolin'g' the separated dyestuff is filtered off by sution; washed-with methanoP-and-dried. There are obtained 28-parts of a blue powder 'which dissolves in concentrated 'stllfuric acid giving a greenish brown coloration and which dyes cotton, regenerated cellulose or polyamide fibers blue shades from a black-red vat.

Example 7 A mixture of 29 parts of l.4-diamino-2-acetylanthraquinone, 14.7 parts of 2-(2'.4'-dichlorphenyl)-4.6-dichlor- 1.3.5-triazine and 500 parts of nitrobenzene is slowly heated to 170 C. while stirring and this temperature is maintained for 2 hours. After cooling the separated dyestuif is filtered off by suction, washed with methanol and dried. There are obtained 35.5 parts of a blue microcrystalline powder which dissolves in concentrated sulfuric acid giving a greenish brown coloration and which dyes cotton, regenerated cellulose and polyamide fibers from a blackred vat blue shades with good fastness properties.

wherein R stands for a radical selected from the class consisting of phenyl, 3'-methylphenyl, 4'-1nethylphenyl, 2'-methoxyphenyl, 3-methoxyphenyl, 4'-methoxyphenyl,

4'-chlorphenyl and 2'4'-dichlorphenyl.

2. The vat dyestufi of the formula I N/ \N o N 1 II N 0 0 ([.LCH3 GHQ-ii NH: NH!

3. The vat dyestutf of the formula *7 t a i 0 N 0 /i: N I

0 I ii-CH1 OKs-l] NH: NH!

4. The vat dyestufl' of the formula OCH:

H N N I! 1 1 II N O I II 0 )OH; CH j NH: NH:

5. The vat dyestutf of the formula OCH| I N *7 N C\ /i? N O II 0 O -A-CHI CH;&

8 NE: NH:

6.. The vat dyestuff of the formula H N/ H 1: 5 I I l 0 I II O &---CH: CHa- NH: NH:

References Cited in the file of this patent UNITED STATES PATENTS 

1. A VAT DYESTUFF OF THE GENERAL FORMULA 